Oxidized chlorinated olefin polymer



UNITED STATES PATENT OFFICE 2,181,158 oxmrzsn on omm'ran omrm POLYMER William J. Sparks, Grantord, and Clifford W.

Muessig, Elizabeth, N, J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing. Application-November 30, 1938,

Serial No. 243,096

11 Claims. (CL 260-94) This invention relates to synthetic iso-clefin normal paint and lacquer solvents. In addition polymer substances, and relates particularly to the polymer which has been both oxidized and polymer substances which have been oxidized and chlorinated retains the high strength characterischlorinated, and especially to high molecular tic of the original polymer, and avoids the brittle,

weight isobutylene polymer substances containfriable character of the ordinary chlorinated 5 ing both oxygen and chlorine. polymer even when relatively high percentages Valuable polymer substances of high molecular of chlorine such as 20% to 50% are reacted into weight are produced by a reaction consisting of the polymer molecule. g the polymerization of iso-olefins, such as iso-' Thus an object of the invention is to modify butylene, by means of boron trifiuoride, alumithe physical characteristics of iso-olefin polymer 10 num chloride and similar catalysts, at low temsubstance in the direction of increasing its soluperatures, that is polymers are produced showing bility, n r sing its compa ibili y with the standmolecular weights ranging from 800 to 250,000 or ard varnish gums and resins, and increasing its more, which polymers are in general of an oily, strength.

plastic or rubbery character depending upon the n Practicing the invention, the hy r carbon l5 molecular weight. They have valuable propergases obtained from the cracking operation which ties for various purposes, but are found to be ing is applied to crude-petroleum are fractionated to compatible with many of the natural and synyield a substantially pure isobutylene material. thetic resins, and insoluble in many of the desir-' This isobutylene mat ri l is h n polymerized by able solvents, particularly oxygen-containing I contact with boron fluoride at temperatures rang- 2o solvents such as the ethers, the ketones, the aling from 10 C. to -l00 0., preferably in an cohols, acetone and similar oxygen-containing inert diluent-refrigerant. The resulting polymer .solvents. This characteristic interferes with material has a molecular weight ranging from many uses of the substances to whichthey might 800 to 250,000 or more, depending upon the purity 2 otherwise be applied. of the isobutylene and the polymerization tem- It has been found that by the application to perature, the purer the material and the lower the polymer of suitable re-agents such as nitric the temperature, the higher the molecular weight acid, ozone, and mixed nitric and sulphuric acids, of the'resulting polymer. I at elevated temperatures, a controlled oxidation The polymer material is then treated with reaction may be obtained with the polymer submixed nitric and sulphuric acids. This treatment 30 stance of any molecular weight, and that the rewith mixed acids may be applied directly to the suiting oxidized polymer substance shows many isobutylene polymer, or it may be applied to the new, useful and valuable properties. polymer dissolved in a suitable solvent such as It has also been found possible to chlorinate the carbon tetrachloride or other inert solvent matesame original iso-olefin polymer and still other rial such'as the saturatedliquid hydrocarbons of useful substances are attainable by the chloriappropriate boiling point. The treatment with nation reaction. However, when a large amount mixed acids is desirably conducted at a temperaof chlorine is introduced into the polymer subturebetween about 95 C.-and 135 C. At temst it n s to e ome nduly brittle and to peratures below 95- 100 C. the oxidation reaco los P y Strength, thereby reducing s utility tion is undesirably slow, while at temperatures for some purposes. above 125-135 0., the amount of depolymeriza- The present invention is based upon the distion of the polymer may be excessive, and an un covery that the iso-olefln poly r n be first X- desirable amount of charrlng of the material may idiz and t e ehlelinated, and that the reoccur. An oxidation reaction occurs between the sultins Oxy r n P ymer compound h oxygen from the nitric acid and the polymer, to 45 still other n w. s l and unexpected p p yield an oxidized polymer which may contain ties. As compared to the unoxidized, unchlorifrom 0.1% to 30% of oxygen according to the nated poly r, the w polymer s readily 80111- amount and concentration of the acids present his in ketones and ester t y,' i. and the length of time the reaction is allowed to o Pr cip from 511011 Solution by the addltlon continue. The exact nature of the combination a of low molecular weight alcohols or by water sowhich occurs B t the polymer and t xy.. lutions Of the 316011015. Furthermore, it is comgen is not definitely knqwn'but is believed Da l w Substantially all Of the Synthetic and that esters, alcohols, acids and ketones of the natural varnish gums and resins, being soluble polymer are formed.

in and compatible with substantially all of the The resulting oxidized polymer maybe washed 55 to remove excess acid, and then treated with the chlorine. If desired the chlorine treatment may be conducted in the same hydrocarbon solvent if such is used, but it is preferably dissolved in a 5 chlorine-containing solvent such as chloroform or carbon tetrachloride or mixtures of the two. The chlorination reaction proceeds directly either in the light or in the dark, and catalysts of any sort are not necessary. However, some improvement in the reaction may be obtained by the use of catalysts such as sunlight, aluminum chloride or iodine monochloride as such or as formed by dissolving iodine in the chloroform solution andreacting it with the first of the added chlorine, or

5 other similar catalysts.

A considerable amount of control of the 'character of the chlorination reaction can be obtained by modification of the temperature at which the reaction occurs, by modification of the speed of chlorination, or the rate at which the chlorine is added, and by the amount of light or catalyst applied to the reacting substances. The very high molecular weight, and the accompanying very high physical dimensions of the polymer molecule leave it subject to depolymerization as the result of a good many different causes, and there is some tendency on the part of the chlorine to cause a depolymerization of the polymer to lower molecular weight substances. This depolymerization efiect is more pronounced at higher temperatures and in the dark. Accordingly if a material of moderate to low molecular weight 'is desired, and the starting material is of high molecular weight, it is possible to degrade or depolymerize the material to the desired extent by chlorinating at an elevated temperature, and chlorinating in the dark. Alternatively, if the maximum molecular weight is desired, with as little depolymerization as possible occurring,

low temperatures and in a strong light, both of which favor the maximum molecular weight. The exact reasons for this control are not as yet known, but it may be that the limited depolymerization which occurs in the presence of light is due to the more rapid chlorination reaction, and the resulting greatly reduced concentration of dissolved, uncombined chlorine element in the solution.

The chlorination reaction proceeds with the liberation of considerable quantities of hydrochloric acid, indicating that the chlorine displaces hydrogen atoms. It does not appear that any substantial amount of oxygen is displaced from thepolymer molecule.

The chlorination reaction may be interrupted when a relatively small amount of chlorine has been combined with thepolymer, or it may be continued to completion, for the addition of amounts of chlorine ranging between 1% and 30% or more; the maximum amount of chlorine being determined by the amount of oxidation previously occurring.

When the desired amount of chlorine has been introduced, the chlorinated product may be separated from the solvent by precipitation with alcohol, in which instance a fractional precipitation may be utilized to separate more highly portions, or for the separation of depolymerized vent may be removed by evaporation or steam the chlorination may be conducted at relativelychiorinated portions from less highly chlorinated mass of the chlorinated material as the residue.

Example 1 A portion of polymer substance prepared as above described having a molecular weight of 13,000 in the amount of 400 grams, is treated with 600 cc. of nitric acid mixed with 50 cc. of sulphuric acid. The reaction continues with the evolution of heat, and the reaction vessel is desirably cooled to keep the temperature between C. and C. to prevent charring or other injury to the polymer, The reaction may continue with stirring over a period of 48 hours, and at the close of the reaction time, the acid may be separated from the oxidized polymer.

Preferably the oxidized polymer is separated from the acid directly but it may be extracted with a solvent, and appropriate purification treatment may be applied as desired.

The purified oxidized polymer having aweigli t of approximately 450 grams is then preferably dissolved in a mixture of 500 cc. of carbon tetrachloride and 500 cc. of chloroform, and the chlorine bubbled through the solution for a period of 1-2 hours until approximately 65 grams of chlorine have been absorbed yielding a polymer containing about 14% of chlorine,

The solvents may then be removed by volatilization and recovered in appropriate manner it desired.

The resulting polymer is found to have a molecular weight ranging between 11,000 and 13,- 000, depending upon the temperature of oxidation, and the temperature of chlorination, since both the oxidation reaction and the chlorination reaction tend to depolymerize the original polymer to some extent and therefore reduce its molecular weight.

The resulting oxidized-chlorinated polymer shows a substantial gainin tensile strength and in crushing strength with relatively slight rubbery characteristics, thereby being in contrast to the original polymer. Furthermore the product is substantially non-tacky and substantially free from stickiness.

The resulting polymer may be satisfactorily mixed with most of the usual varnish gums, resins and drying oils such as linseed oil, copal, cellulose esters, dammar, etc., and it is soluble in and compatible with most of the varnish solvents such as turpentine, the hydrocarbon liquids, acetone, benzene, ether, etc.

Example 2 The polyisobutylene polymer may be prepared as above described, the polymerization being continued to the desired molecular weight, and the polymer may then be dissolved in carbon tetrachloride. Conveniently, 60 grams of polymer may be dissolved in 1,000 cc. of carbon tetrachloride. A steady current of ozone is then blown through the solution for a period of time ranging from 5. to 40 hours. A five-hour period of treatment with ozonized air containing a good amount of ozone may result in the incorporation of from 2% to 4% of oxygen. Treatment for a period of 20 hours may incorporate up to 15% of oxygen, and treatment for 40 hours may incorporate from 30% to 40% oxygen, depending to some extent upon the temperature and the ozone concentration in the ozonized air.

Alternatively, the solution of polyisobutylene may be treated with warm nitric acid, or with warm mixed nitric and sulfuric acids at temper- 1. 4 Ha i? r? if atures below the boiling point of the carbon tetrachloride, or with refluxing at the boiling point.

If the oxidation is conducted with ozone, the oxidized material remains dissolved in the carbon tetrachloride, and when the desired amountof oawgen has been incorporated into the polymer, the passage of ozone may be discontinued, and the chlorine substituted for it, either with or without the addition of chloroform which may if desired be added in the proportion of from 5% to 50% of the oxidized solution. The chlorination may be continued as in Example 1 until the desired amount of chlorine is introduced. Alternatively, if the oxidation has been accomplished by the use of the mixed acids, they are desirably decanted from the solution and the solution washed to remove residual traces of acids. The oxidized polymer may be recovered by evaporationv of the solvent carbon tetrachloride, and thereafter redissolved in a mixture of carbon tetrachloride and chloroform, for chlorination, or the chlorination may be conducted directly upon the washed solution. In either event the chlorine is passed through the solution until the desired amount is reacted into the polymer. The solvent may then be evaporated and the oxidized, chlorinated polymer recovered.

As above pointed out, relatively little is known of the chemical reaction which occurs in the preparation of the substance of this invention. It seems probable that the original polymerization occurs as follows:

If this equation is correct, it shows the resulting polymer to be a linear, substantially saturated hydrocarbon substance containing probably one unsaturated linkage in the carbon chain, as indicated by experimental data.

Still less is known about the oxidation reaction, but it may be that the reaction proceeds as follows:

has been attached to a given carbon atom, no reaction thereafter occurs for the removal of oxygen and'replacement by chlorine. Hence it is probable that only carbon atoms not bound to oxygen atoms participate in the chlorination re- This combination of oxidation and subsequent chlorination is also applicable to the polymer produced by polymerizing together at a low temperature a mixture of polyisobutylene and butadiene. In this instance the reaction proceeds in a manner closely analogous to that of Example 1, to yield a corresponding product.

The oxidized-chlorinated polymer material is thermoplastic but melts over a range of temperature, and is particularly advantageous for thermo-plastic molding either in the pure form, or particularly when mixed with the usual fillers, such as wood flour, dyes, pigments, etc. It is also compatible with rubber, the synthetic rubbers and the various organic plastics, and maybe combined with them to yield many valuable compositions.

Thus the invention provides a new and useful material and product consisting of an oxidizedchlorinated iso-olefin polymer; and the process of polymerizing, oxidizing and chlorinating isoolefln substance and the further process steps of compounding the oxidized-chlorinated polymer with various varnish gums, resins, solvents, etc.

The above presented examples of the invention utilize for the polymer, the simple polymer of isobutylene. The invention is not, however, limited to the use of isobutylene alone as the raw material. There are various other analogous polymers, such as polyethylene, polypropylene, polyamylene and mixed polymers of the several olefinic substances, and these materials also are substantially saturated or nearly saturated linear hydrocarbon polymers of high molecular weight, and they also are similarly reactive under analogous reaction conditions in common with the polyisobutylene' as above described andsimilar advantageous results are obtainable by the oxidation and chlorination steps.

While there are above disclosed but a limited number of embodiments of the material and process of the invention, it is possible to produce still other embodiments of the invention resulting in products of modified properties without departing from the inventive concept above disclosed, and it is therefore desired that only such limitations be imposed upon the appended claims as are stated therein or required by the prior art.

The invention claimed is: 1. A high molecular weight oxidized, chlorinated, olefinic polymer.

2. A high molecular weight oxidized, chlorinated, iso-oleflnic polymer.

- 3. A linear isobutylene polymer containing substituted oxygen and chlorine.

4. A high molecular weight, substantially saturated linear hydrocarbon polymer containing oxygen and chlorine.

5. The process of preparing a synthetic substance cdmprising the steps of polymerizing an iso-olefln to a high molecular weight, oxidizing the polymer, and thereafter chlorinating the oxidized polymer.

6. The process ofpreparing a synthetic substance comprising the steps of polymerizing isobutylene to a high molecular weight, oxidizing the polymer, and thereafter chlorinating the oxidized polymer.

'7. The process of preparing a synthetic substance comprising the steps of polymerizing isobutylene to a high molecular weight, and oxidizing the polymer by the application thereto of mixed nitric and sulphuric acids.

8. The process of preparing a synthetic substance comprising the steps of treating isobutylene in solution at a low temperature with a polymerizing catalyst, separating the polymer from the solution and catalyst, oxidizing the polymer by treatment with mixed nitric and sulphuric acids at a temperature ranging between C. and C., removing the acids, and treating the oxidized polymer in solution with chlorine.

9. The process of preparing a synthetic substance comprising the steps of treating isobutylene in solution at a low temperature with a polymer- I izing catalyst, separating the polymer from the solution and catalyst, oxidizing the polymer by treatment in solution in a non-oxidizable solvent with mixed nitric and sulphuric acids at a temperature ranging between 90 C. and 135 0., removing. the acids, and treating the oxidized polymer in solution with chlorine.

10. The process of preparing a synthetic sub-' stance comprising the steps of treating isobutylene in solution at a low temperature with a polymerizing catalyst, separating the polymer from the solution and catalyst, oxidizing the polymer by treatment in solution in a non-oxidizable solvent with mixed nitric and sulphuric acids at a temperature ranging between 90 C. and 135 C., removing the acids, and treating the oxidized polymer in solution with carbon tetrachloride.

11. The process of preparing a synthetic substance comprising the steps of treating isobutylene in solution at a low temperature with a polymerizing catalyst, separating the-polymer from the solution and catalyst, oxidizing the polymer by treatment in solution with ozone and treating the oxidized polymer in solution with elemental chlorine.

WILLIAM J. SPARKS.

CLIFFORD W. MUESSIG. 

